Process of making an amino phenyl anthraquinone



Patented Oct. 20, 1942 T v UNITED STATES PAjT ENT oFFIcE PROCESS or MAKING AN AMINO PHENYL ANTHRAQUINONE Paul Kranzlein, Leverkusen-I. -G.-Werk, Germany, assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Original application February 25,,

1938, Serial No. 192,564. Divided and this application November 28, 1940, Serial No. 367,592.

In Germany February 27, 1937' v 2Claims. (owed-37s) The present invention relates to amino-phenyl anthraquinones and the corresponding aroylbenzoic acids and to a process of preparing the same.

. I' have found that primary amines containing a diphenyl linkage and corresponding with the following general formula wherein the nucleus containing .theamino group may contain further substituents, X1 and X2 representing hydrogen or standing together for the group:

om, \NH, N a1kyl, o. s or n CH or derivatives or salts of such amines may be condensed, in the presence of an acid condensing agent, such as aluminum chloride or zinc chloride, with phthalic anhydride or a substitution product thereof. There are formed, witha good yield, the corresponding aroyl-benzoic acids which, in the same or in another process, may be further condensed to form the anthraquinon'e derivatives. Such smooth condensations with phthalic anhydrides could not be'foreseen. It was rather to be supposed, that the free primary base would react with the phthalic anhydride,

especially in the presence of aluminium chloride, to form an acylation product or a phthalanil. By the new reaction it is possible to prepare a great number of hitherto unknown anthraquinone derivatives or the corresponding aroyl-benzoic acids which are very valuable in the manufacture of dyestuffs. For instance by sulfonation; of the anthraquinone derivatives there are obtainedacid wool dyestufis. The following examples serve to illustrate the invention, but they are not intended to limit it thereto. The parts are by weight, unless otherwise stated. The relationship between parts by weight and parts by volume is that which'exists between a kilo and a liter.

l'. 9 parts of 3-methyl-4-aminodiphenyl are run, at 120 0., into a melt of 120 parts of sodium chloride-aluminium chloride while stirring. The reaction mixture is allowed to cool to 110 C. and 8 parts of phthalic anhydride are added. On addition of the latter, the temperature rises quickly. As the reaction temperature must by no means surpass 120 C., the whole is preferably somewhat cooled or the phthalic anhydrideis added in small portions. The temperature is then maintained while well stirring for 30-45 minutes at 110 C.- 115 C, Within this period of time, the 3-methyll-aminodiphenyl has reacted with the phthalic anhydride to form the corresponding benzoyl- 'benzoic acid. The temperature is then raised to neutral and dried in a drying oven. The yield amounts to more than The crude red product may easily be further purified by sublimating of recrystallizing it. From glacial acetic acid the 3'-methyl-4'-amino-2-phenyl-anthra quinone crystallizes in the form of red needles which have the constant melting point of 199 C.

.2. 11 parts of 3-methyl-4-amino-diphenyl hydrochloride are introduced, while stirring at a temperature of 120 C., into a melt of 120 parts oi'sodium chloride-aluminium of chloride. The reactionmixture is then allowed to cool to C. and8 parts of phthalic anhydride are added. The temperature is, for 30-45 minutes, kept at 110 C.- C., then raised andthe, whole is further stirred, for 1% hours, at 150"155 C. The melt is worked up as described in Example 1. By recrystallization from glacial'acetic acid, the 3'- methyl-4-amino-Z-phenyl-anthraquinone, melting at 119 C., is obtained.

3. 10 parts of 3-methyl-4-amino-diphenyl are introduced, at 120 C., into'a melt of 120 parts of sodium chloride-aluminium chloride. The whole is then allowed to cool to 110 C. and 10 parts of ortho-chlorophthalic anhydride are added in portions. While well stirring, the temscribed in the preceding examples.

quinone thus obtained forms a dark red vat and dissolves in concentrated sulfuric acid to a dark red solution. 1

4. 9 parts of 4-aminodiphenyl are introduced, at 120 C., into a melt of 120 parts of sodium chloride-aluminium chloride. 8 parts of phthalic anhydride are added in portions, at a temperature of 110 C. The whole is stirred for 40 minutes at 110 C.-1l5 C. and, thereupon, for

1% hours, at 150 C. After workingup the melt, a crude rust brown product is obtained which forms a red vat and dissolves in concentrated sulfuric acid to a red solution. The 4'-amino- Z-phenyl-anthraquinone may easily be sublimated. When recrystallizing it from chlorobenzene, it is obtained in the form of long red needles which have the constant melting point of 221 C. Sulfonated with fuming sulfuric acid containing 20% of sulfuric anhydride, the dyestufi dyes wool orange tints.-

5. 10 parts of 2-amino-carbazole and 9 parts of phthalic anhydride are melted with 120 parts of sodium chloride-aluminium chloride, as de- The temperature of the melt is maintained, for 30 minutes, at 110 C.-115 C. and the whole is then further stirred, for one hour, at 150 C. After working up as described above, a crude redbrown product is obtained which may easily be sublimated. The phthaloyl-Z-amino-carbazole of the following probable constitution dissolves in concentrated sulfuric acid to a pure blue solution and forms a reddish-green vat. Recrystallized from trichlorobenzene, it is obtained in the form of red needles melting at 355 C. Sulfonated with fuming sulfuric acid containing 20 per cent of sulfuric anhydride, the dyestuff dyes wool yellow-brown tints.

6. 10 parts of 3-amino-N-ethylcarbazol and 8 parts of phthalic anhydride are melted with 120 dissolves in concentrated sulfuric acid to a greenish-blue solution and yields a green vat. The product may easily be Sublimated and when recrystallized from trichlorobenzene it is obtained in the form of violet needles melting at 296 C. Sulfonated with fuming sulfuric acid containing 20% of sulfuric anhydride, the dyestuff dyes wool light-brown tints.

7. 10 parts of 2-amino-diphenylene oxide and 8 parts of phthalic anhydride are melted'with 120 parts of sodium chloride-aluminium chloride. The melt is then stirred for 30 minutes, at C. and, thereupon, for 1%; hours at 150 C. After working up, a crude red-brown product is obtained which yields a red vat and dissolves in concentrated sulfuric acid to a red solution. The phthaloyl-2-amino-diphenylene oxide probably has the following constitution:

* o o p...

It is further purified by sublimation. Red needles are thus obtained which sinter at a temperature of 295 C. and melt, while slowly decomposing, at a temperature above 300 C. Sulfonated with fuming sulfuric acid containing 20% of sulfuric anhydride, the dyestuff dyes Wool orange tints.

8. 10 parts of 3-amino-phenanthrene and 9 parts of phthalic anhydride are melted with parts of sodium chloride-aluminium chloride. The melt is first stirred for 45 minutes at 110 C. and, thereupon, for 1% hours, at C. After working up and subliming, the phthaloyl-3- amino-phenanthrene of the following probable constitution is obtained in the form of red crystals which have the constant melting point of 291 C. They dissolve in concentrated sulfuric acid to a redviolet solution and yield a red vat. Sulfonated with fuming sulfuric acid containing 20% of sulfuric anhydride, the dyestulf dyes wool brown tints.

9. 9 parts of 2-amino-fiuorene and 8 parts of phthalic anhydride are melted with 120 parts of sodium chloride-aluminium chloride. The melt is first stirred for 40 minutes, at 110 C. and, thereupon, for 1 hours at 150 C. After working up and subliming the product formed, the

phthaloyl-2-amino-fluorene of the following probable constitution:

NH2 cm is obtained in the form of red crystals melting at 293 C. It dissolves in concentrated sulfuric acid to a red solution and yields a red vat. Sulfonated with fuming sulfuric acid containing 20 per cent of sulfuric anhydride, the dyestuff dyes Wool orange-red tints.

10. 12 parts of 3-acetamino-N-ethyl-carbazole and 8 parts of phthalic anhydride are introduced, at a temperature of 115 C., into a melt of 120 parts of sodium chloride-aluminium chloride. The whole is further stirred for 15 minutes at 115 C. and, thereupon, for one hour at C.

The melt is worked up as described above, a yellow-brown crude product being obtained. The phthaloyl-3-acetamino N+ethyl-carb'azole of I the following probable constitution:

dissolves in concentrated sulfuric acid to a bluegreen solution and yields a yellow-green vat. Recrystallization from trichlorobenzene, it is obtained in the form of yellow crystals melting at 352 C. The acetamino compound may be saponified in the usual manner.

11. parts of 3-benzoylamino-N-ethyl-carbazole and 8 parts of phthalic anhydride are introduced at 115 C. into a melt of 120 parts of sodium chloride-aluminium chloride. The whole is further stirred, for 15 minutes, at 115 C, and, thereupon, for one hour at 155 C. After Working up as described above a crude brown product is obtained. The phthaloyl-B-benzoyl-amino-N- ethylcarbazole dissolves in concentrated sulfuric acid to a blue solution and yields a yellow-green vat. Recrystallized from trichlorobenzene, it is obtained in the form of yellow crystals melting at 336 C. 4

12. 113 parts of 4-acetamino-3-methyl-diphenyl are introduced while well stirring at a temperature of 105 C.110 (3., into 1200 parts of molten sodium chloride-aluminium chloride (mixing proportion: 350 parts of NaCl-2000 parts of A1C13). 80 parts of phthalic anhydride are then added in small portions at the same temperature within 10 minutes. The reaction is complete as soon as a test portion of the product on addition of caustic soda solution dissolves nearly entirely in water, which is the case after about 5 minutes. The melt is then poured on ice and 150 parts by volume of concentrated hydrochloric acid are added. The mixture is thoroughly boiled,

whereby the reaction product agglomerates to a ball. The solution is decanted, the ball is finely triturated and boiled with water until and after cooling, the reaction product is obtained in the form of grains.

It is then dissolved in dilute sodium carbonate solution, boiled, filtered from some undissolved matter and the filtrate is precipitated by means of hydrochloric acid. After filtering with suction, washing until neutral and drying, 168 parts of light yellow 4 ortho carboxy) benzoyl 3'- methyl-4'-acetamino-diphenyl, melting at 228 C.-230 C. are obtained. For further purification the keto-carboxylic acid is boiled with 750 parts by volume of alcohol, allowed to cool, filtered with suction, washed with a small amount of alcohol and dried. There remain 155 parts of 4 (ortho carboxy) benzoyl-3'-methyl-4-acetaminodiphenyl melting at 238 C.-240 C. The yields amount to 84% of the theoretical.

155 parts of 4-(ortho-carboxy)-benzoyl-3- methyl-4acetaminodiphenyl are introduced into 800 parts by volume of sulfuric acid monohydrate and heated, for 4-5 hours, at 110 C.120 C. After cooling, the solution is poured on ice, the yellow-green sulfate of 3'-methyl-4'-amino2- phenyl-anthraquinone which separates is filtered with suction and washed with water. The still moist sulfate is introduced into 4000-5000 parts by volume of a caustic soda solution of 3-5 per cent strength at boiling temperature. The product is filtered with suction and washed with hot water, until the filtrate is colorless. After drying, 120 parts of 3'-methy1-4-amino-2-phenylanthraquinone melting at 192 C. are obtained. The yield amounts to 92% calculated upon 4-(ortho' carboxy) benzoyl-3-methyl-4-acetaminodiphenyl. By recrystallizing the product from glacial acetic acid it is obtained in the form of red needles melting at 198 C.

13.- parts of 4-acetamino-diphenyl are introdu'ced, while stirring, into a melt of 400 parts of sodium chloride-aluminium chloride, at a temperature of 120 C. The whole is allowed to cool to C. and 35 parts of phthalic anhydride are added in small portions. On addition of the phthalic anhydride, the temperature quickly rises. Since the reaction temperature must not surpass -110 (2., the phthalic anhydride is added in small portions. As soon as all of the phthalic anhydride has been introduced, the whole is further stirred, for 5 minutes, at C. The melt is then poured onto ice, whereby the lightyellow 2-(4"- acetamino 4-phenyl benzoyl) benzoic acid separates.- In order to dissolve the aluminium salts, the reaction mixture is strongly acidified by means of dilute hydrochloric acid, boiled and filtered with suction. For further puri-' fication the crude product is again boiled with water in order -to dissolve any phthalic acid which may be present. A sufficient amount of dilute sodium carbonate solution is added to the residue. The whole residue, thereby, dissolves, in case the melt has been properly formed. Some animal char coal is then added, the whole is boiled and filtered through a filter. The filtrate is acidified by means of dilute hydrochloric acid, the white 2- (4 -acetamino-4 -phenyl-benzoyl) benzoic acid separating in a very pure form. The whole is filtered with suction, the residue is washed until neutral and dried in a drying oven at about 100 C. The yield amounts to 65 grams which corresponds to more than 90% of the theoretical. For further purification, the acid is either immediately after filtering with suction or after drying, heated for hour, on the steam bath under reflux, with about 500 parts by volume of methanol, in order to dissolve unimportant impurities. After cooling and filtering with suction, the 2-(4"-acetamino-4-phenyl-benzoyD-benzoic acid is obtained in a very pure form. It is very suitable for further chemical reactions, especially for ring closure with formation of 4'-amino-Z-phenyl-anthraquinone. The melting point of the pure acid (recrystallized from alcohol) is 256 C.

80 parts of 2-(4"-acetamino-4-phenyl-ben zoyD-benzoic acid are introduced into 400 parts by volume of sulfuric acid monohydrate and heated, while stirring, for 4 -5 hours at a temperature of C. It is then allowed to cool and poured on ice, whereby the greenish-yellow sulfate of 4'-amino-2-phenyl-anthraquinone separates. The whole is heated and the sulfate is filtered with suction. It is then introduced into 2000 parts of a caustic soda solution of 3-5% strength. The blood-red 4'-amino-2- phenyl-anthraquinone is immediately formed. The alkaline suspension is boiled and filtered with suction. The residue is washed until neutral by means of hot water, until the filtrate is light-red. The residue is dried. The yield amounts to 65 grams which corresponds to 96% of the theoretical. Recrystallized from chlorobenzene,,the product is obtained in' the form of long, red needles melting at 221 C.

14. 106 parts of 2-acetylamino-diphenyl are introduced while well stirring, into 1200 parts of molten sodium chloride-aluminium chloride (mixing proportion: 350 parts of NaCl-2000 parts of A1013), at a temperature'of 105 C.-110 C. 80 parts of phthalic anhydride are then added in small portions at the same temperature within 10-15 minutes. The reaction is complete as soon as a test portion of the product, on addition, of caustic soda solution, dissolves nearly entirely in water, which is the case after about minutes. The batch is worked up and the crude product is purified as described in Example 12. 142 parts of 4-(ortho-carboxy)-benzoyl- 2-acetylamino-diphenyl, melting at 245 C.248 C., are thus obtained. The yield amounts to 79% of the thecrectical.

110 grams of l-(ortho-carboxy)-benzoyl-2- ,acetylamino-diphenyl are introduced into 500 parts by volume of sulfuric acid mono hydrate and heated, for 1 -2 hours, at 110 C.-120 C. After working up, as described in Example 12, there are obtained 84 parts of a crude product namely a mixture of 2f-amino-Z-phenyl-anthraquinoneand 2-acetylamino-2-pheny1-anthraquinone. The well dried and finely pulverized product is introduced into 350 parts by volume of acetic anhydride at 80- 90 C. and the whole is heated to boiling for half an hour. 200 parts by volume of dichlorobenzene are then added, the whole is boiled and filtered while hot. The 2'-ac'etylamino-2-phenyl-anthraquin0ne which separates in the form of well-defined crystals from the cooled filtrate, is filtered'with suction and washed with alcohol.

This application is a divisional of application Serial No. 192,564, filed February 25, 1938, Patent No. 2,281,583.

I claim: I

1. The process of producing a diphenyl amine the nucleus of which is substituted by a radical selected from the class consistingoi the radicals of phthalic anhydride and the chlorine substitu- ',tion products thereof which comprises. condensing at a temperature above C. in the presence of aluminium chloride a primary amino compound of the general formula wherein Y represents a member of the group consisting of hydrogen and methyl with a substance selected from the class consisting of phthalic anhydride and the chlorine substitution products of phthalic anhydride.

' 2. The. process of producing a phthaloyl .diphenyl amine which comprises condensing at a temperature of at first about C. and later about C. in the presence of aluminium. chloride a primary amino compound of the general formula NHZ wherein Y represents a member of the group consisting of hydrogen and methyl with a substance selected from the class consisting of phthalic anhydride and the chlorine substitution products of phthalic anhydride.

PAUL KRANZLEIN. 

